Production of aniline via anthranilate

Patent metadata

Field	Value
Publication number	US-10173969-B2
Application number	US-201515120163-A
Country	US
Kind code	B2
Filing date	Feb 19, 2015
Priority date	Feb 20, 2014
Publication date	Jan 8, 2019
Grant date	Jan 8, 2019

Abstract

The invention relates to a method for producing aniline, comprising the steps of: a) providing o-aminobenzoate, wherein said o-aminobenzoate comprises anthranilate anion and a suitable cation, b) converting said anthranilate anion to aniline by thermal decarboxylation in the presence or absence of a catalyst, c) extracting the aniline produced in step b) in an organic solvent at least once, and d) purifying the aniline produced in steps b) and c) by distillation, wherein said distillation produces aniline and a water phase.

First claim

The invention claimed is:

1. A method for producing aniline, comprising:
a) providing an aqueous solution of o-aminobenzoate, wherein said o-aminobenzoate comprises anthranilate anion and NH 4 + and/or Na + as cation,
b) converting said anthranilate anion to aniline by thermal decarboxylation in the presence or absence of a catalyst, and either
c1) purifying the aniline produced in step b) by distillation if the content of aniline in the aqueous solution obtained in method step b) is above 120 g/l, or
c2) extracting the aniline obtained in method step b) at least once in an organic solvent before purifying the aniline by distillation if the content of aniline in the aqueous solution obtained in method step b) is not more than 120 g/l.

2. The method of claim 1 , wherein said o-aminobenzoate is provided chemically or produced biologically.

3. The method of claim 1 , wherein step a) to step c1) or step c2) are run continuously.

4. The method of claim 1 , wherein said catalyst is a heterogeneous acid catalyst.

5. The method of claim 1 , wherein said catalyst is a heterogeneous base catalyst.

6. The method of claim 1 , wherein the extraction of aniline in an organic solvent in step c2) is performed for more than one time for a further pre-concentration of aniline in advance of distillation.

7. The method of claim 1 , further comprising recovering the organic solvent used in the extraction of step c2).

8. The method of claim 1 , wherein said organic solvent is selected from the group consisting of alcohols, phenols, amides, ethers and aromatic hydrocarbons.

9. The method of claim 1 , wherein the NH 4 + cation is recovered as NH 3 subsequent to the distillation of step c1) and re-fed to the fermentation of step a).

10. The method of claim 2 , wherein said o-aminobenzoate is produced biologically by fermentation of a raw material comprising at least one fermentable carbon substrate using a recombinant microbial host cell capable of converting said raw material comprising a fermentable carbon substrate to o-aminobenzoate by fermentation.

11. The method of claim 10 , wherein said recombinant microbial host is removed prior to the subsequent conversion of said anthranilate anion to aniline by thermal decarboxylation in step b), wherein said removed recombinant microbial host preferably is re-fed to the fermentation of step a).

12. The method of claim 10 , further comprising a further step e) of re-feeding the water-phase of the extraction performed in step c) and/or re-feeding the water-phase of the distillation performed in step d) to the fermentation of step a).

13. The method of claim 10 , wherein the raw material of step a) is selected from the group consisting of sugar beet, sugar cane, starch-containing plants, lignocellulose, glycerol and C1-compounds.

14. The method of claim 10 , wherein said fermentable carbon substrate is selected from the group consisting of C-5 monosaccharides, C-6 monosaccharides, disaccharides, and tri-saccharides.

15. The method of claim 10 , wherein said recombinant host is selected from the group consisting of bacteria, yeast and fungi.

16. The method of claim 10 , wherein said fermentation of step a) is a batch fermentation, a fed-batch fermentation or a continuous fermentation.

17. The method of claim 4 , wherein said heterogeneous acid catalyst comprises a zeolite.

18. The method of claim 17 , wherein said zeolite comprises zeolite H—Y.

19. The method of claim 5 , wherein said heterogeneous base catalyst comprises a layered double hydroxide.

20. The method of claim 19 , wherein said layered double hydroxide comprises Mg—Al hydrotalcite.

21. The method of claim 7 , wherein the recovering comprises distillation.

22. The method of claim 7 , wherein recovered organic solvent is re-fed to step c2).

23. The method of claim 8 , wherein said organic solvent comprises an alcohol comprising 1-dodecanol.

24. The method of claim 13 , wherein the raw material of step a) comprises a starch-containing plant comprising corn.

25. The method of claim 13 , wherein the raw material of step a) comprises a lignocellulose comprising straw, wood, and/or bagasse.

26. The method of claim 13 , wherein the raw material of step a) comprises a C1-compound comprising CO.

27. The method of claim 14 , wherein said fermentable carbon substrate comprises a C-5 monosaccharide comprising xylose and/or arabinose.

28. The method of claim 14 , wherein said fermentable carbon substrate comprises a C-6 monosaccharide comprising glucose, fructose, and/or mannose.

29. The method of claim 14 , wherein said fermentable carbon substrate comprises a disaccharide comprising saccharose.

30. The method of claim 14 , wherein said fermentable carbon substrate comprises a trisaccharide comprising ketose.

31. The method of claim 15 , wherein said recombinant host comprises bacteria comprising Eschericha coli strain, a Corynabacterium strain and/or a Pseudomonas strain.

32. The method of claim 31 , wherein said bacteria comprises a Corynabacterium strain comprising Corynabacterium glutamincum .

33. The method of claim 32 , wherein said Corynabacterium glutamincum comprises Corynabacterium glutamincum ATCC 13032.

34. The method of claim 31 , wherein said bacteria comprises a Pseudomonas strain comprising Pseudomonas putida.

35. The method of claim 34 , wherein said Pseudomonas putida comprises Pseudomonas putida KT2440.

36. A method of using aniline produced by the method of claim 1 , comprising converting the aniline to methylenedianiline using formaldehyde in the presence of water and catalyst.

37. A method of using methylenedianiline produced by the method of claim 36 , comprising converting the methylenedianiline to methylenediisocyanate using phosgene.

Assignees

• Covestro Deutschland Ag

Inventors

• Jaeger Gernot
• Magnus Jorgen
• Moussa Amgad Salah

Classifications

• C12P13/001

  Amines; Imines · CPC title

• C12P13/00 Primary

  Preparation of nitrogen-containing organic compounds · CPC title

• C12P7/40 Primary

  containing a carboxyl group {including Peroxycarboxylic acids} · CPC title

• C07C265/12

  having isocyanate groups bound to carbon atoms of six-membered aromatic rings · CPC title

• C07C263/18

  Separation; Purification; Stabilisation; Use of additives · CPC title